Developing accelerators for silver halide emulsion layers



United States Patent Ofi 7 3,129,100 Patented Apr. 14, 1964 ice 3,129,100 DEVELGPING ACCELERATDRS FQR SILVER HALIDE EMULSIUN LAYERS Herbert Grabhiifer, Cologne-Flittard, Horst Schiller, Munich, and Hans Ulrich and August Randolph, Leverlrusen, Germany, assignors to Agta Aktiengesellschaft, Leverkusen, Germany, a corporation of Germany No Drawing. Filed Mar. 13, 1962, Ser. No. 179,472 Claims priority, application Germany Mar. 16, 1%1

6 Claims. (Cl. 96-66) This invention concerns a new class of developing accelerators which are chemically characterized by at least one quaternary nitrogen atom substituted by a cyanoethoxyethyl radical as well as a process for developing silver halide emulsion layers.

It has long been known that quaternary nitrogen compounds are able to accelerate photographic development, whether as an additive to the developer or to the emulsion. It was originally assumed that the effect depends on the action of the cation on surface tension, such as can be produced for example by longer aliphatic radicals. As shown by subsequent investigations this limitation is not necessary (see for example Angewandte Chem, vol. 67, page 523 (1955)).

All onium salts are similar in their action to the quaternary nitrogen compounds, for example quaternary phosphonium or ternary sulphonium salts. charged onium groups may be present in the molecule.

It is also known that this action of the onium compounds is obtained with systems which are sensitized with polyalkylene oxides; the emulsions used can also be spectrally sensitized. Moreover, intramolecular linkages of polyalkylene oxides with quaternary ammonium salts have been briefly described.

The effect of the acceleration of the development which has been referred to can be explained according to T. H.

James, Photographic Science and Technique, vol. 1913.

(1953), page 35, by the fact that the negatively charged bromine ion shell which exists around the silver halide grain is neutralized by the onium cations thus facilitating access of the negatively charged developer anions for example the hydroquinone anion with a double negative charge in an alkaline medium which is normally made difiicult because of electrostatic repulsion of said ion shell. The higher the charge on the developer anion, the greater is the shortening of the latent period by the addition of suitable quaternary salts.

In conformity with this theory, onium salts are most highly effective as development accelerators when alkali developers containing solely hydroquinone as developer compound are used.

Some of the known onium salts still show a good accelerating effect with the super additive metol-hydroquinone development system which is of importance in practice, but scarcely any effects with strongly super additive systems such as 1-phenyl-3-pyrazolidone/hydroquinone or p-arninophenyl-3-aminopyrazoline/hydroquinone. With the last-mentioned system, in which for example the l-p-aminophenyl-3-aminopyrazoline enters into a reciprocal action with the silver halide grain and thus constitutes the reaction which determines the speed of development, a further increase in the speed of development was not to be expected on account of the already very short latent periods per se (see Phot. Science and Engin., vol. 4, page 225 (1960)).

It is among the objects of the instant invention to provide compounds which further accelerate the development and shorten the latent period even with strongly super additive developer systems.

It has now been found that considerable acceleration One or more effects can still be produced if the development is carried out in the presence of quaternary nitrogen compounds of the general formula:

R, o in which R and R stand for alkyl, aralkyl, phenyl, cyanoethyl, or cyanoethoxyethyl or for methylene groups or atoms necessary for completing a heterocyclic ring such as morphohne, piperidine and the like; R represents alkyl,

aralkyl, phenyl, cyanoethoxyethyl or a radical selected from those having the following general formulae wherein R and R have the meaning specified above; X represents any desired anion, such as a halide, toluenesulfonate or alkyl sulphate anion. It may be pointed out that the anion is not especially critical and is selected according to the requirements of the special composition or emulsion in which the compound is to be used; m is an integer from 2-5, n from 26 and p from 1-100, preferably 1-7.

The ethylene oxide chains of the compounds represented by the above general formula can be replaced with other alkylene oxide chain such as propylene oxide or butylene oxide chains.

The excellent and surprising eiiicacy of the compounds according to the invention as well as their superiority over similar known products rests apparently on the action of the cyanoethyl and cyanethyl oxethyl radicals.

The quaternary salts can either be added to the developer or to the emulsion or to both simultaneously.

The acceleration effect of the compounds according to the invention is not restricted to certain types of emulsions or developers. It is also apparent with color developers containing aromatic amine developing compounds or with emulsions containing optical or chemical sensitizers such as sulphur compounds, salts of precious metals such as ruthenium, rhodium, palladium, iridium or platinum, furthermore, iodine salts, reducing agents, polyalkylene oxides, mercuric compounds, stabilizing agents such as compounds of the azaindene series, e.g., 4-hydroxy-6-methyl-1,3,3a,7-tetra-azaindene. The accelerators according to the invention can also be advantageously used with fixing developers. They may also surprisingly be used at the same time as anti-fogging agents.

Examples of the new development accelerators are those of the fellowing constitution:

I Q HPI POHPOHPo-orn-onioN or- (has Diethy hbenzyl-cyanoethoxyethyl-amnronium chloride III Di- (n-butyl) -benzy1-eyanoethoxyethyl-ammonium chloride 7 The aforementioned quaternary salts may be prepared as follows:

COMPOUND I (a) N,N-Dimethyl-N-Cyanoethoxyethylamine (b) Dimethyl-Phenethyl-Cyanoethoxyethyl-Ammonium Chloride 14.2 g. of the aforementioned amine (Ia) and 14 g. of 2-chloroethyl benzene are heated while stirrmg for 2 hours to 150 C., 100 cc. of acetone and the quantity of ethanol (about 10 ml.) necessary for forming a solution are then added. On cooling, 88 g. of quaternary salt with a melting point of 123 C. crystallize out.

COMPOUND 11 (a) N,N-Diethyl-N-Cyanoethoxyethylamine 117 g. of diethylaminoethanol and 100 g. of sodium hydroxide are dissolved in 250 cc. of water and 53 g. of acrylonitrile are added dropwise while stirrlng at 45 C. The mixture is left standing for 5 hours at room temperature and is then extracted by shaking three times with methylene chloride, using 250 cc. on each occasion. After distilling off the methylene chloride, an oil is left which is fractionated in vacuo.

B.P. 134 C./ 16 torr. Yield: 105 g.

(b) Diethylbenzyl-Cyanoethoxyethyl-A mmonium Chloride 12.5 g. of benzyl chloride and 14.6 g. of the aforementioned amine (Ila) are heated for 2 hours while stirring to 150 C. The mixture is stirred with 50 cc. of acetone with heating and cooled with iced water. Crystals with a melting point of 91 C. are obtained.

Yield: 12 g.

COMPOUND III (a) N,N-Dibutyl-N-Cyanoethoxyethy[amine 2 g. of sodium methylate are dissolved in 173 g. of di-n-butylethanolamine and 53 g. of acrylonitrile are added while stirring at 35 C. The mixture is left for 6 hours at room temperature and is then stirred with 200 cc. of water, cc. of 25 percent sodium hydroxide solution and 500 cc. of methylene chloride. 155 g. of amine with the boiling point 169 C./ 13.5 torr are recovered from the methylene chloride phase after vacuum distillation.

(b) Di-n-Butyl-Benzyl-Cyanoethoxyethyl-Ammonium Chloride 12.7 g. of benzyl chloride and 22.6 g. of the aforementioned amine (Illa) are heated in 50 ml. of dry toluene for 16 hours to boiling point. The crystals precipitating on cooling are suction-filtered and washed with ether.

M.P. 160 C. Yield: 8 g.

COMPOUND IV Dim ethyl-( p -Chlorobenzy l-Cyanoethoxyethy l-Ammonium Bromide 14.2 g. of N,N-dimethyl-N-cyanoethoxyethylamine (Ia) and 20.5 g. of 4-chlorobenzy1 bromide are thoroughly mixed at room temperature. After 1 hour, crystals have separated out, and these are washed with acetone.

M.P. 133 C. Yield: 30 g.

COMPOUND V Dim ethyl-4-Nitrobenzy l-Cyanoethoxyethyl- Ammonium Chloride 14.2 g. of N,N-dimethyl-N-cyanoethoxyethyl (Ia) and 17.1 g. of p-nitrobenzyl chloride are heated for 5 hours under reflux in 50 cc. of acetone. The precipitated crystals are suction-filtered and recrystallized from a mixture of acetone and alcohol (10.1).

M.P. 144-145 C. Yield, 22 g.

COMPOUND VI (a) N-Methyl-N,N-Di(Cyanoethoxyethyl -A mine 119 g. of N-methyl-N,N-di-(fl-hydroxyethyl)-amine and 10 g. of sodium hydroxide are dissolved in 250 cc. of water and 106 g. of acrylonitrile are added thereto at 45 C. within 1 hour. The mixture is left for 8 hours at room temperature. Thereafter, 30 g. of sodium hydroxide are added and the amine precipitated as an oil is taken up in methylene chloride. After distilling off the methylene chloride, the amine is fractionated in vacuo.

B.P. 160-'170 C./0.9l.5 torr. Yield, 55 g.

(b) M ethyl-4-Chlorobenzyldi (Cyanoethoxyethyl Ammonium Bromide 21.9 g. of the aforementioned amine (VIa) and 20.5 g, of p-chlorobenzyl bromide are heated for 1 hour to 150 C. The mixture is thereafter stirred with 50 cc. of acetone at boiling temperature. The product crystallized out is washed on a suction filter several times with acetone.

M.P. 159 C. Yield: 32.5 g.

COMPOUND VII Di n Butyl Phenethyl Cyanoethoxyethyl- Ammonium Chloride 22.6 g. of N,N-di-n-butyl-N-cyanoethoxyethyl-amine (111a) and 14 g. of B-chlorethyl benzene are heated under reflux for 6 hours in 50 cc. of dry toluene. After standing for 15 hours at room temperature, crystals are separated out and these are suction-filtered and washed several times with ether. M.P. 158 C. Yield: 16 g.

COMPOUND VIII Diethyl Phenethyl Cyanoethoxyethyl-Ammonium Chloride 17 g. of N,N-diethyl-N-cyanoethoxyethyl amine (Ha) and 14 g. of ,B-chlorethyl benzene are heated for 6 hours in 30 cc. of dry toluene to boiling point. After standing for 15 hours at room temperature, the precipitated oil is separated out and treated with acetone. The crystals which are thereby formed are suction-filtered and washed several times with ether.

M.P. 70 C. Yield: 12 g.

COMPOUND IX Dibutyl p Clzlorobenzyl Cyanoethoxyethyl- Ammonium Bromide 22.6 g. of N,N-di-(n-butyl)-N-cyanoethoxyethyl amine (HM) and 20.5 g. of p-chlorobenzyl bromide are heated for 30 minutes to 150 C. After standing for 8 hours at room temperature, the product is dissolved while hot in acetone and precipitated with ether.

Crystals have a melting point of C. Yield 25 g.

COMPOUND X Dimethyl-n-Octyl-Cyanoethoxyethyl-Ammonium Bromide 14.2 g. of N,N-dimethyl-N-cyanoethoxyethyl-amine (Ia) and 19.3 g. of n-octyl bromide are heated for 2 hours to 9 100 C. The reaction product is recrystallized from acetone.

M.P. 98-99 C. Yield: 21 g.

COMPOUND XI Diethyl-n-Octyl-Cyanoelhoxyethyl-Ammonium Bromide 17 g. of N,N-diethyl-N-cyanoethoxyethyl amine (Ila) and 19.3 g. of n-octyl bromide are heated for 2 hours to 100 C. After standing for 24 hours in a refrigerator, the product is triturated with ether and suction-filtered.

MP. 5558 C. Yield: 20 g.

COMPOUND XII Dimethyl-n-Ddecyl-Cyan0ethoxyethyl-Ammonium Bromide 14.2 g. of N,N-dimethyl-N-cyanoethoxyethyl amine (Ia) and 24.9 g. of dodecyl bromide are heated for 2 hours to 100 C. The reaction product is recrystallized from acetone.

MP. 107 C. Yield: 28 g.

COMPOUND XIII 1,6-Hexamethylene-Bis-[N,N,N'-Tetramethyl-N,N'-Di- (Cyanoethoxyethyl ]-Amm0nium Bromide 14.2 g. of N,N-dimethyl-N-cyanoethoxyethyl amine (Ia) and 12.2 g. of 1,6-dibromohexane are heated for 2 hours to 100 C. The reaction product is recrystallized from a mixture of acetone and alcohol (:2).

MP. 144 C. Yield: 21 g.

COMPOUND XIV .l,6-Hexamethylene-Bis-[N,N,N',N'-Tetraethyl-N,N-Di- (Cyanoethoxyethyl) ]-Amm0nium Bromide 17 g. of N,N-diethyl-N-cyanoethoxyethyl amine (Ila) and 12.2 g. of 1,6-dibromohexane are heated for 2 hours to 100 C. After adding 50 cc. of acetone, the mixture is heated for 1 hour under reflux, cooled and suctionfiltered. Recrystallization takes place from acetone/alcohol (10:2).

MP. 151 C. Yield: 12 g.

COMPOUND XV (a) N,N-Di(Cya 0ethyl)-N-(Cyan0eth0xypropyl)Amine (b) N,N-Di (Cyanoethyl) -N-4-Chlorobenzyl-N-(Cyanoeth0xypropyl)Amm0nium Bromide 4.7 g. of N,N-di(cyanoethyl)-N-(cyanoethoxypropyl) amine (XVa) and 4.1 g. of p-chlorobenzyl bromide are heated for 3 hours to 150 C.; the product is then treated with acetone and precipitated with ether.

MP. 127 C. Yield: 2.8 g.

COMPOUND XVI E Zhylenc-B is-[N ,N ,N ',N -T etra-M ethyl-N ,N -Di- (Cyanoethoxyethyl ]-A mmonium-Bromide Prepared according to Compound XIII using 1,2-dibromoethane as starting compound.

COMPOUND XVII (a) Diethylene-Glycol-Di-Methane-Snlphonic Acid E ter 114.5 g. of methane-sulfo-chloride are added in portions at 0 C. to a solution of 53 g. of diethtylene glycol in 200 .cc. of dried pyridine. After stirring for 1 hour at 10 C. the mixture is poured on ice water, acidified with aqueous hydrochloride, separated with common salt and shaken three times each with 300 cc. of methylene chloride. The collected methylene chloride extracts are dried with sodium sulphate and evaporated. Crystals are obtained having a melting point of 5556 C. after recrystallization from alcohol.

(b) Ethoxyethyl ot,w Bis [N,N,N',N etramethyl- N,N-Di-(Cyanoethoxyethyl)] Ammonium Methane Sulfonate 26.2 g. of di-ethylene glycol di-methane sulfonic acid ester (XVIIa) and 28.4 g. of fl-cyanoethoxyethyl-N-dimethylamine (Ia) are mixed and heated on an oil bath for 4 hours to a temperature of 120 C. The reaction mixture is extracted three times with hot benzene for separating undesired side products, dissolved in methyl alcohol and this solution clarified with active carbon, bleaching earth and again with active carbon. The filtrate is completely evaporated. After heating to C. in vacuo, 39 g. of a yellowish viscous sirupy liquid remain.

Yield 71 percent of the theory.

A 20 percent aqueous solution is used for photographic applications.

COMPOUND XVIII (a) T riethylene Glycol Di-p-Toluene SulfOnic Acid Ester 75 g. of triethylene glycol dissolved in 200cc. of dried pyridine are reacted with 190 g. of toluene sulpho-chloride at 0 C. Further processing is accomplished according to Example XVII. A crystallized compound is obtained which melts after recrystallization from ethanol at 73-74 C.

(b) Di (Ethoxy) Ethyl oc,w Bis [N,N,N,N Tetramethyl N,N Di (Cyanoethoxyethylfl Ammonium-p-Toluene Sulfonate 45.2 g. of triethylene glycol di-p-toluene sulphonic acid ester (XVEIIa) and 28.4 g. of fi-cyanoethoxyethyl-N-dimethylamine (Ia) are heated for 4 hours to a temperature of C. The reaction mixture is further processed as described in Example XVIIc. 50 g. (68 percent of the theory) of a yellow colored sirupy liquid are obtained.

COMPOUND XIX (a) Ethoxy ethyl 0..., Bis [N,N-Dimethyl-N,N,N',N- Tetra-(Cyanoethoxyethyl)JAmmonium-Methane Sulfanate 10.4 g. of diethylene glycol di-methane sulfonic acid ester (XVIIa) and 17.2 g. of di-(fl-cyanoethoxyethyl)-N- methylamine (VIa) are thoroughly mixed, heated in an Oll bath for 45 hours at C. and thereafter further processed as described in Example XVIIc. 21 g. (74 percent of the theory) of a yellowish brown sirupy liquid are obtained.

COMPOUND XX Di (Ethoxy) Ethyl cc,w Bis [N,N' Dimethyl N,

N,NN' Tetra (Cyanoethoxyethylfl Ammonium- Toluene Sulfonate 45 g. of triethylene glycol di-p-toluene sulfonic acid ester (XVIIIa) and 45 g. of di-(fi-cyanocthoxyethyl)-N- methylamine (VIa) are heated for 5 hours to a temperature of 120 C. and further processed as described in Example XVIIc. 58.5 g. (65 percent of the theory) of a yellowish brown sirupy liquid are obtained.

COMPOUND XXI (a) y-Cyan0eth0xypr0pyl-N,N-Di(Cyanoethyl)-Amine 159 g. of acrylonitrile are added in portions with stirring at 45 C. to a solution of 75 g. of 3-aminopropanol- (1) and 10 g. of sodium hydroxide in 250 cc. of water. After stirring for 8 hours the mixture is shaken three times with 250 cc. of methylene chlorideeach. The collected extracts are washed 'with 50 cc. of water, dried 11 with sodium sulphate, filtrated and evaporated. The residue is fractionated in vacuo.

B.P. 160 C./0.5 torr.

(b) Ethoxyethyl ot,w Bis [N,N,N,N' T etracyanethyl- N,N' Di (Cyanoethoxypropylfl Ammonium-Methane Sulfonate 47 g. of y-cyanoethoxypropyl-NN-dicyanethyl-amine (XXIa) and 26.2 g. of diethylene glycol di-methane sulfonic acid ester (XVIIa) are heated for 4 hours at 120 C. and further processed according to Example XVIIc. 52 g. (71 percent of the theory) of a yellowish brown sirupy liquid are obtained.

COMPOUND XXII (a) Diethyl-Cyanoetlzoxypentyl-Amine (b) Di (Ethoxy) Ethyl a,w Bis [N,N,N',N'-Tetraethyl N,N' Di (Cyanoethoxypentyl)]-Arnmniump-Toluene Sulfonate 42.4 g. of diethyl-cyanoethoxypentyl-amine (XXHa) and 45.2 g. of triethylene glycol di-p-toluene sulfonic acid ester (XVIIIa) are heated for 5 hours to 120 C. Further processing is accomplished as described in Example XVIIc. 55 g. (63 percent of the theory) of a yellowish brown sirupy liquid are obtained which solidifies on supercooling to the waxy product.

COMPOUND XXIII Di-(Ethoxy)-Ethyl ta,w-Bis-N,N'-[Hexa-(Cyanoethoxyethyl) ]-A mmonium-p-Toluene S ul fonale 61.6 g. of tri-(cyanoethoxyethyl)-amine (described in United States Patent No. 2,326,721) and 45.2 g. of triethylene glycol di-p-toluene sulfonic acid ester (XVIIIa) are heated for 5 hours to 120 C. and further processed according to Example XVIIc. 80 g. (75 percent of the theory) of a high viscous product are obtained.

COMPOUND XXIV Di (Ethoxy) Ethyl a,w Bis [N,N' Diethyl N,N- Diphenyl N,N Di (Cyanoethoxyezhylfl Ammonium p Toluene Sulfonate 46.4 g. of fi-cyanoethoxyethyl-N-phenyl-N-ethyl amine (described in United States Patent No. 2,326,721) and 45.2 g. of triethylene glycol di-p-toluene sulfonic acid ester (XVIHa) are heated for 5 hours to 120 C. and further processed according to Example XVIIc. 57.2 g. (62.5 percent of the theory) of a yellowish brown viscous prod net are obtained.

COMPOUND XXV (a) Eth0xyethyl-a,w-Bis-[N,N,N',N-Tetra-Betyl-N,N'-Di (Cyanoethoxyethyl -Amm0nium-M ethane S ul fonate 45.2 g. of dibutyl-cyanoethoxyethyl amine (111a) and 26.2 g. of diethylene glycol di-methane sulfonic acid ester (XVIIa) are heated for 4-5 hours to 120 C. and further processed according to Example XVIIc. 50 g. (70 percent of the theory) of a yellowish brown sirupy liquid are obtained.

COMPOUND XXVI Di- (Ethoxy)-Ethyl-u,w-Bis-[N,N-Di-(Cyanoethoxyethyl) ]-M0rpholinium-p-Toluene Sulfonate 36.8 g. of fi-cyanoethoxyethyl-N-morpholine (described in United States Patent No. 2,326,721) and 45.2 g. of tri- 12 ethylene glycol di-p-toluene sulfonic acid ester (XVIIIa) are heated for 5 hours to C. and further processed according to Example XVIIc. 5-1.5 g. (63 percent of the theory) of a resinous yellowish colored product are obtained.

COMPOUND XXVII (a) Octaethylene Glycol Di-Metlmne Sulfonic Acid Ester 114 g. of methane sulpho-chloride are added in portions at 0 C. to a solution of g. of octa-ethyleneglycol in 200 ml. of dried pyridine, whereby the reaction temperature in the flask should not exceed 5 C. The mixture is stirred for 1 /2 hours at room temperature and thereafter poured onto 500 g. of ice. The resulting mixture is acidified with hydrogen chloride, saturated with common salt and extracted with methylene chloride. The organic product is separated, clarified with active carbon and bleaching earth and evaporated. The residue represents a yellowish brown viscous product which does not crystallize.

Yield 197 g. (75 percent of the theory).

(1)) Hepta-(Ethoxy)-Ethyl-oc,w Bis [N,N,N',N' Tetraethyl-N,N'-Di-(Cyanoethoxyethyl J-Ammonium-Methane Sulfonate 51 g. of diethyl-cyanoethoxyethyl-amine (Ila) and 52.7 g. of octaethylene glycol di-methane sulfonic acid ester (XXVIIa) are heated with stirring for 3 hours at 120 C. and further processed according to Example XVIIc. 65 g. (75 percent of the theory) of a yellowish brown sirupy liquid are obtained.

COMPOUND XXVIII Hepta- (Ethan )-Ethyl-tz,w-Bis-[N,N' Dimethyl N,N,N', N-Tetra-(Cyanoethoxyethyl)] Ammonium Methane Sulfonate 45 g. of di-(cyanoethoxyethyl)-N-methylamine (VIa) and 52.7 g. of octaethylene glycol di-methane sulfonic acid ester (XXVIIa) are heated with stirring for 4 hours to 120 C. and further processed as described in Example XVIIc. 66.5 g. (68 percent of the theory) of a yellowish brown sirupy liquid are obtained.

COMPOUND XXIX Hepta-(Ethoxy)-Ethyl-a,w-Bis-[N,N,N',N-Tetraethyl N, N'-Di (Cyan0eth0xypentyl)] Ammonium Methane Sulfonate 42.4 g. of diethyl-cyanoethoxypentyl-amine (XXIIa) and 52.7 g. of octaethylene glycol di-methane sulionic acid ester (XXVIIa) are heated with stirring for 4 hours to 120 C. and further processed according to Example XVIIc. 62 g. (65 percent of the theory) of a yellowish brown sirupy liquid are obtained.

COMPOUND xxx H epta- (Ethoxy -Ethyl-ix,w-Bis-[N ,N '-Di- Cyanocthoxyethyl) -M orpholini um-M ethane S ul 1 onate 36.8 g. of cyanoethoxyethyl-N-morpholine (described in United States Patent No. 2,326,721) and 57.2 g. of octaethylene glycol di-methane sulfonic acid ester (XXVIIa) are heated with stirring for 3 hours to 120 C. and further processed as described in Example XV IIb. 64.5 g. (72 percent of the theory) of a resinous yellowish brown product are obtained.

COMPOUND XXXI Hepta-(Ethoxy)-Ethyl-oz,w-Bis-[N,N' Diethyl N,N' Diphenyl-N,N' Di (Cyanoethoxyethyl)] Ammonium- Methane Sulfonate 46.4 g. cyanoethoxyethyl-N-phenyl-N-ethyl amine (de scribed in United States Patent No. 2,326,721) and 52.7

g. of octaethylene glycol di-methane sulfonic acid ester (XXVIIa) are heated with stirring for 3 hours to 120 1.3.. C. and further processed according to Example XVIIc. 67.5 g. (68 percent of the theory) of a yellowish brown sirupy liquid are obtained.

The following examples illustrate the effect of the compounds according to the invention. With comparable development times, the accelerator elfect is expressed as an increase in sensitivity.

EXAMPLE 1 A negative gelatino-silver bromiodide emulsion with a silver coating of 4.5 g. of Ag/m. and an iodine content of 66 mmol/mol of Ag and also a content of 920 mg. of 4-hydroxy-6-methyl-l,3,3a,7-tetrazaindene is divided into two portions (A-l-B). Portion A is cast on a cellulose triacetate film; to portion B are added 0.6 g. of the oleyl polyether derived from 20 mols of ethylene oxide and 1 mol of oleyl alcohol. The resulting emulsion is also cast on a cellulose triacetate film.

The layers are exposed to light behind a stepped wedge with a logarithmic density increase of 0.15 and developed for 5 and 10 minutes, respectively, at 20 C. in a developer of the following composition:

Water to make 1000 cc.

The layers are thereafter fixed and rinsed.

Under the same conditions, the same layers are developed in developers which contain the substances referred to in the following table in addition to the above composition:

RESULTS WITH EMULSION A AFTER A DEVELOPMENT TIME OF 5 MINUTES Addition, Sensi- Speeimen g./l. Fogging tivity, 'y 2 degrees Control 0. 06 0. 54 l 0. 06 +2 0. 67 Comparative compound 1 0.8 0. 06 0.50 1 0.06 +2 0.72 Comparative compound 2 0.7 0.06 0 0. 54 1 0. 08 +2 0. 62 Comparative compound 3 0.8 0. 06 0 0. 54

RESULTS WITH EMULSION A AFTER 10 MINUTES DEVELOPMENT Control 0. 07 0. 78 XIII 1 0. 09 +1. 0. 90 Comparative compound 3.--. 3 0.8 0. 08' 0 0.78 1 0. 07 +2 0. 90 Comparative compound 2 4 0. 7 0 07 0 0 82 RESULTS WITH EMULSION B AFTER A DEVELOPMENT TIME OF 5 MINUTES RESULTS WITH EMULSION B AFTER 10 MINUTES DEVELOPMENT 0.08 0. 90 1 0. 08 +1 0. 98 0. 7 0. 09 0 0. 90 1 0. 09 +2 0. 91 Comparative compound 3 0.8 0. 21 -1 0.83

1 The differences in sensitivity are indicated in degrees DIN; S=0.1 over fogging was selected as measurement point.

B The gradation was measured as a straight line between the measure ment points S=0.5 and 1.5 over fogging.

3 Equimolar to XIII.

Equimolar to II.

The comparative compounds have the following chemical constitution:

COMPARATIVE COMPOUND 1.-DIME-THYL-PHEN- ETHYL-fi-HYDROXYETHYL-AMMONIU M CHLORIDE -8.5 g. of N,N-dimethylaminoethanol and 14 g. of wchlorethyl benzene are heated for 2 hours to C. The

reaction product is recrystallized from acetone/alcohol Melting point: 9293 C. Yield: 16 g.

COMPARATIVE COMPOUND 2.DIETHYL-BENZYL-B- HYDROXYETHYL-AMMONIUM CHLORIDE 17.8 g. of N,N-dirnethyl-aminoethanol and 24.4 g. of 1,6-dibromohexane are heated for 2 hours to 100 C. The reaction product is recrystallized from alcohol.

Melting point: 179-180 C. Yield: 30 g.

EXAMPLE 2 An orthochromatically sensitized miniature film strip (Agfa Agepe) exposed behind a stepped'wedge is developed'for 3 minutes at 20 C. in a developer having the following composition:

G. Anhydrous Na SO 50 Hyroquinone 6.5 Anhydrous Na CO Y I I 40 NaBr 5 1-phenyl-3-pyrazolidone 0.3

Water to make 1000 cc.

The strip is thereafter fixed and rinsed.

Under the same conditions, the same film is developed in a developer which additionally contains 0.25 g. of the Compound VI per litre.

Addition, Sensi- Spectmen g./l. Fogglng tivity, 1

degrees Control 0.05 2. 9 VI 0. 25 0. 3 +2 3. 5

1 Sensitivity at S=1. Z Gradation between the measurement points S=0.7 and 2.0.

EXAMPLE 3 A panchromatically sensitized minature film strip (Agfa Isopan IFF exposed behind a stepped wedge is developed for 3 minutes at 20 C. in a developer having the following composition a I Anhydrous Na SO 50 Hydroquinone 1 6.5 Anhydrous N21 CO I 40 NaBr 5 1-phenyl-3-pyrazolidone Q 0.3 Water to make 1000 cc.

The strip is then fixed and rinsed.

15 Under the same conditions, the same film is developed in a developer which also contains 0.8 of the Compound IV per litre.

A highly sensitive film (Agfa X-ray dental film) coated on both sides and disposed beneath an aluminium step, is exposed with X-ray radiation and developed for 3 minutes at 20 C. in the developer referred to in Example 2. Under the same conditions, the same film is developed in a developer which also contains 0.25 g. of the sub- An orthochromatically sensitized miniature film strip (Agfa Agepe) exposed behind a stepped wedge is developed for 3 minutes at 20 C. in a developer having the following composition:

Anhydrous Na SO 50 Hydroquinone 6.5

Anhydrous Na Co 40 NaBr 5 l p-aminophenyl 3-amino-A -pyrazoline-dihydrochloride 0.2

Water to make 1000 cc.

The strip is then fixed and rinsed.

Under the same conditions, the same film is developed in a developer which also contains 0.8 g. of the substance IV per litre.

Addition, Sensi- Speeimen g./l. Foggrng tivity, 'y 1 degrees Control 0. O8 3.0 0 8 0. 06 +2 3.0

1 1 As in Example 2.

EXAMPLE 6 A highly sensitive film (Agfa X-ray dental film) coated on both sides and disposed beneath an aluminum step is exposed to X-ray radiation and fixed and developed for 7 minutes at 20 C. with vigorous movement in a combined fixer and developer of the following composition:

Anhydrous Na SO; g 30 Hydroquinone g 14 1-phenyl-3-pyrazolidone g 0.5 Na PO .l2H O g N32S203.5H20 g- NaBr g Normal sodium hydroxide solution ..cc 50 Water to make 1000 cc.

In the same way, the same film is developed in the 15 (Agfa Agepe) exposed behind a stepped wedge is fixed and developed with brisk moving in a combined fixer and developer of the following composition for 7 minutes at C.:

20 Anhydrous Na SO g 30 Hydroquinone g... 14 l-phenyl-3-pyrazolidone "g" 0.5 N33PO4.12H2O g--. NazszowsHgo g NaBr g 10 Normal sodium hydroxide solution cc 50 Water to make 1000 cc.

Under the same conditions, the same film is developed in a combined fixer and developer which also contains 0.5 g. of the substance II per litre.

Addition, Sensi- Specimen g./1. Fogging tivity,

degrees Control 0. 05 1. 8

1 2 As in Example 2.

EXAMPLE 8 A panc-hromatically sensitized miniature film strip (Agfa Isopan IFF) exposed behind a stepped wedge is fixed and developed for 7 minutes at 20 C. with vigorous movement in a combined fixer and developer of the following composition:

Anhydrous Na SO g 30- Hydroquinone g 14 l-phenyl-3-pyra.zolidone g 0.5 Na PO .12H O g 60 Na S O 5H O g..- NaBr g 10 Normal sodium hydroxide solution cc 50 Water to make 1000 cc.

Under the same conditions, the same film is developed in a combined fixer and developer which also contains 0.25 or 0.5 g. of the substance II per litre.

Addition, Sensi- Speeimen g./l. Fogging tivity,

degrees fifii ffiii::::::::::::::: ain 3:33 $5.2 ii II 0.5 0.26 +3 113 1 2 As in Example 2.

EXAMPLE 9 A highly sensitive film (AGFA X-ray dental film) coated on both sides and disposed beneath an aluminium step is exposed with X-ray radiation and fixed and developed for 7 minutes at 20 C. with vigorous movement aforementioned combined fixer and developer, which also contains the substances I, VII or Addition, Sensi- Speeirnen g./l. Fogging tiv1ty, 'y 2 degrees 1 2 As in Example 2.

EXAMPLE 7 An orthochromatically sensitized miniature film strip 17 in a combined fixer and developer having the following composition:

Anhydrous Na SO g 30 Hydroquinone g 14 1-( p-aminophenyl -3-amino-A -pyrazolinedihydrochloride g 0.3 Na3PO4-12H2O g Na2S203.5H2O g 50 NaBr g Normal sodium hydroxide solution cc 50 Water to make 1000 cc.

Under the same conditions, the same film is developed in a combined fixer and developer which also contains the substances II, III, VII, or VIII.

A color positive film strip (Agfa Color Positive Cinefilm Type S) exposed behind a stepped wedge is developed for 8 minutes at C. in a color developer of the following composition:

G. Diethyl-p-phenylene diamine sulphate 2.75 Hydroxylamine sulphate 1.2 Anhydrous sodium sulphite 2.0 Sodium hexametaphosphate 2.0 Anhydrous potassium carbonate 75 Potassium bromide 2.0

Water to make 1000 cc.

After the usual further processing by means of a bleaching bath and fixing bath, a measurable color wedge is obtained.

Under the same conditions, the same film is developed in the above developer, which also contains the substances I or II. The accelerating eifect is apparent from the following table:

Addition, Sensi- Specimen g./l. Fogglng tivity, 7 1

degrees 1 Sensitivity measured at 8:01 over fogging. Z Gradation measured between the measurement S=0.7 and 2.0 over fogging.

NorE.-y=ye1low, m=magenta, c=eyan.

EXAMPLE 11 A silver bromide paper (Agfa Brovira Normal 1) exposed behind a stepped wedge with a logarithmic density increase of 0.1 is developed for 60 seconds at 20 C. in a developer of the following composition and fixed and rinsed in the usual manner.

G. Anhydrous sodium sulphite 13 Hydroquinone 3 Monomethyl-p-amino-phenol 1 Anhydrous soda 26 KBr 1 Water to make 1000 cc.

18 Under the same conditions, the same paper strip is developed in a developer which also contains 0.2 g. of the Compound XIII per litre. The strip has the sensitivity and gradation of the comparison strip after 50 seconds; at 60 sec. it shows a sensitivity which is higher by one step.

EXAMPLE 12 A panchromatically sensitized gelatino-silver bromiodide negative emulsion, containing 0.35 mol of silver halide per litre of casting solution and having a sensitivity of 21 DIN was divided into two portions.

Portion A was cast as a comparison test with a casting thickness of 11,41. on a cellulose triacetate support, provided with a subbing layer.

Portion B had added thereto 1.5 g. of the Compound II per litre of casting solution and was cast with the same layer thickness.

Both film samples, after exposure behind a grey stepped wedge, were developed under comparable conditions as regards temperature and movement in a developer having the following composition:

G. Ortho-hydroxyethylaminophenolsulphate 7.5 Anhydrous sodium sulphite 1 00 Anhydrous soda 10 KBr 0.4

Water to make 1000 cc.

RESULTS OF THE DEVELOPMENT AFTER 12 MINUTES DEVELOPMENT TIME AT 20 C.

Sensitiv- Grada- Fogglng ity, tlon degrees Control PortlonA 0.5 0.10 Portion B +1 0.8 0.11

RESULTS OF THE DEVELOPMENT AFTER A DEVELOP- MENT TIME OF 24 MINUTES AT 20 C.

Control Portion A 0.85 0.13 Portion B +1.5 0.25 0.13

EXAMPLE 13 A panchromatically sensitized photographic film (Agfa Isopan IFF) is exposed through a test wedge, developed for 10 minutes at 20 C., fixed and washed. The developer has the following composition:

Samples of the same photographic material are processed under the same conditions with the only exception that the developer additionally contains a certain amount of the Compounds XVII-XX. The improving of the sensitivity is indicated in degrees DIN; as measurement point is selected 3:0.2 over fogging. The gradation is measured as a straight line between the measurement point S=0.5 and 1.5 over fogging.

Improve- Addition, ment of Sample g./l. Sensi- 'y Fogging tivity, degrees Improve- Additlon, ment of Sample g./l. Sensi- 'y Fogging tivlty, degrees EXAMPLE 15 A silver bromiodide gelatine negative emulsion (66 millimols AgI/Mol AgBr) which is not additionally sensitized is cast on a cellulose triacetate support. The resulting layer has a silver content of 4.5 g. Ag/nm The material is exposed through a test wedge and developed for 1 minute at 20 C. in a developer having the following composition:

G. Hydroquinone 3 Na SO anhydrous 20 Phenidone (l-phenyl-S-pyrazolidone) 0.4 Na CO anhydrous 20 KBr 1 Benzotriazole 0.1

Water to make 1000 cc.

Comparative tests with developers which additionally contain Compounds XV II-XX show the following results:

Improve Addition, ment of s-l Fvsglng 9 9. 9 3 5 630305 UIOIQUIOJ EXAMPLE 16 G. Na SO anhydrous 70 Borax 7 Hydroquinone 3.5 Metol (p-methylaminophenol sulfate) 3.5 Sodium citrate 7 KBr 0.4

Water to make 1000 cc.

After the usual processing (fixing, washing, drying) the following results are obtained:

Strips of said two film materials were exposed Improve- Additlon, ment of Sample g./1. Sensiv Fogglng tivity,

degrees EXAMPLE 17 Similar results as in Example 16 are obtained if the following developer composition is used:

G. Na SO anhydrous 50 Hydroquinone 6.5 Na CO anhydrous 40 1 (p amino-phenyl)-3-amino-A -pyrazoline-dihydrochloride 0 2 Water to make 1000 cc.

The following result was obtained:

Improve- Addition, merit of Sample g./kg.. e s 1 ar Emulsion tivity,

degrees EXAMPLE 18 The following example demonstrates the superiority of the compounds whose use is specified in the present invention in comparison with corresponding compounds which contain no cyanoethoxy radical. The tests were performed with the film material described in Example 15. The negative film is developed for 5 minutes at 20 C. with the developer described in Example 13. After the usual fixing and washing, the following results were obtained:

The comparative compound hepta-(ethoxy)-ethyl-a,wbistriethylammonium-methane sulfonate:

is used.

The compound is prepared according to the following instructions: 52.7 g. of octaethylene glycol di-methane sulfonic acid ester (XXVIIb) and 40.4 g. of triethyl amine are refluxed for 5 hours in 50 cc. of acetone. After evaporating the solvent and the excess of triethylamine, the reaction mixture is extracted for three times with benzene, dissolved in methanol and treated with active carbon, bleaching earth and again with active carbon. After evaporating in vacuo 59 g. (81 percent of the theory) of a yellowish brown-colored highly viscous oil are obtained. A 20 percent aqueous solution is used for the photographic test.

EXAMPLE 19 A strip of a color-positive-film (Agfa-color-positive cinefilm type S) is exposed through a test wedge and developed for 8 minutes at 20 C. with a color-forming developer having the following composition:

Water to make 1000 cc.

A strip of the same film material is processed under the same conditions with the only exception that the de- 21 veloper composition described above contains additionally a certain amount of the Compound XXVIII. The following results are obtained:

1 Sensitivity measured at S= 0.2 over fogging. 2 Gradation measured between the measurement :S=O.7 and 2.0 over fogging.

EXAMPLE 20 A silver bromiodide gelatine emulsion having an iodide content of 60 mmol/mol Ag which contains a cyan coupler of the naphthol series for example Z-(N-methyl-N- n octadecyDamino sulfo 1 hydroxy 2 naphthanilide is divided in three portions.

Portion A is cast on a suitable support with a thickness of the layer of 5 1. To portion B is added 0.5 g. of the Compound XX/kg. of emulsion. To portion C is added 0.5 g. of the Compound XXVIII/kg. of emul- S1011.

The resulting layers of B and C have also a thickness of 5,u. The three samples are exposed through a test wedge and developed under the same conditions for 8 minutes in the color-forming developer described in Example 19. After the usual further processing by means of a bleaching and fixing bath the following results are obtained:

A silver bromiodide gelatine emulsion with an iodine content of 40 mmol/mol Ag which contains a magenta coupler of the pyrazolobenzimidazole series for example 3' hepta decyl pyrazolobenzimidazole 5 sulfonic acid (as described in German Patent No. 1,070,030) is processed according to Example 20. It is developed for 14 minutes. The following results are obtained:

Improve- Addition, ment of Sample g. g., Sensl- Fogglng Emulsion tivity, degrees A 1.5 0.13 B 0. 5 +1 1. 5 0. 13 O 0. 5 +1 1. 6 0. 13

1 1 As in Example 19.

Having thus described our invention, we now state that we believe our invention to be capable of numerous variations. For example, the compounds according to the invention can be used in combination with any developer compound or composition known per se; e.g.,

hydroquinone, p-methylarnino phenol, l-phenylpyrazolidone 3 and derivatives thereof, compounds of the 4 aminopyrazolone series, 1 aminophenyl 3 aminopyrazoline and derivatives thereof or color-forming dcvelopers of the p-phenylene diamine type. According to one embodiment of the invention, the development can be accomplished in the presence of silver halide solvents such as water-soluble alkali-metal, alkaline-earthmetal or ammonium thiosulfates, in particular sodium, potassium or ammonium thiosulfate. The compounds according to the invention can be added to the developer composition in an amount of 0101-10 g. per litre or to a silver halide emulsion in an amountof 0.1-10 g. per kg. of emulsion.

What we claim is:

1. In a process for developing an exposed photographic material containing at least one silver halide emulsion layer, the improvement which consists in developing the exposed photographic material in contact with a compound having the formula in which R and R are each a radical of the group consisting of alkyl, phenylalkyl, phenyl, cyanoethyl, and cyanoethoxyethyl and together are the atoms required to complete a heterocyclic radical of the group consisting of morpholino and piperidino; R is a member of the group consisting of alkyl, phenylalkyl, phenyl, cyanoethoxyethyl and radicals having the following formulae wherein m is an integer from 2 to 5, n is an integer from 2 to 6 and p is an integer from 1 to '100; and X is an anion.

2. A process as defined in claim 1 in which the exposed photographic material is developed in contact with a compound having the following formula wherein R and R are each a radical of the group consisting of alkyl, phenylalkyl, phenyl, cyanoethyl, and cyanoethoxyethyl and together are the atoms required to complete a heterocyclic ring, wherein m is an integer from 2 to 5 and p is an integer from 1 to 7, and X is an anion.

3. A process as defined in claim 1 in which the exposed photographic material is developed in contact with a silver halide solvent.

4. A process as defined in claim 1 in which the exposed photographic material is developed in contact with a polyalkylene oxide.

5. A light-sensitive photographic material having at least one light-sensitive silver halide emulsion layer and containing between 0.1 and 10 grams per kilogram of the said emulsion of a compound of the following formula in which R and R are each a radical of the group consisting of alkyl, phenylalkyl, phenyl, cyanoethyl, and cyanoethoxyethyl and together are the atoms required to complete a heterocyclic radical of the group consisting of morpholino and piperidino; R is a member of the group consisting of alkyl, phenylalkyl, phenyl, cyanoethoxyethyl and radicals having the following formulae and in which R and R are each a radical of the group consisting of alkyl, phenylalkyl, phenyl, cyanocthyl, and cy- 24 anoethoxyethyl and together are the atoms required to complete a heterocyclic radical of the group consisting of morpholino and piperidino; R is a member of the group consisting of alkyl, phenylalkyl, phenyl, cyanoethoxyethyl and radicals having the following formulae wherein m is an integer from 2 to 5, n is an integer from 2 to 6 and p is an integer from 1 to 100; and X is an anion.

References Cited in the file of this patent UNITED STATES PATENTS Kaszuba Sept. 20, 1949 2,944,902 Carroll et al July 12, 1960 3,047,389 Dickinson July 13, 1962 

1. IN A PROCESS FOR DEVELOPING AN EXPOSED PHOTOGRAPHIC MATERIAL CONTAINING AT LEAST ONE SILVER HALIDE EMULSION LAYER, THE IMPROVEMENT WHICH CONSISTS IN DEVELOPING THE EXPOSED PHOTOGRAPHIC MATERIAL IN CONTACT WITH A COMPOUND HAVING THE FORMULA 